Effect of Intermolecular Interactions on Metal-to-Metal Charge Transfer: A Combined Experimental and Theoretical Investigation
Effect of Intermolecular Interactions on Metal-to-Metal Charge Transfer: A Combined Experimental and Theoretical Investigation
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分子间相互作用对金属间电荷转移的影响：实验和理论相结合的研究
DOI：
10.1002/anie.201909495
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Tao Liu
中科院分区：
文献类型：
--
作者：
Cheng‐Qi Jiao;Yin‐Shan Meng;Yang Yu;Wen‐Jing Jiang;Wen Wen;Hiroki Oshio;Yi Luo;Chun‐Ying Duan;Tao Liu
了解分子间相互作用对金属间电荷转移（MMCT）的影响对于通过接枝基于MMCT的分子阵列来开发分子器件至关重要。在此，我们报道了一系列无溶剂的{Fe 2Co 2}化合物，它们具有相同的阳离子四核{[Fe（PzTp）（CN）3]2[Co（dpq）2]2}2+（PzTp−=四（吡唑基）硼酸盐，dpq=联吡啶并[3，2-d：2′，3 ′-f]喹喔啉）正方形单元，但具有不同尺寸的阴离子，包括BF 4 −，PF 6 −，OTf−和[Fe（PzTp）（CN）3]−。在{[Fe（PzTp）（CN）3]2[Co（dpq）2]2}2+单元中与钴离子配位的dpq配体之间的π-π相互作用可以通过引入不同的反离子来调节，从而调节CoN 6八面体的畸变和钴离子周围的配位场.这种变化导致不同的MMCT行为。计算分析揭示了不同抗衡阴离子的存在下调谐的分子间相互作用对MMCT行为的实质性作用。
Understanding the effects of intermolecular interactions on metal‐to‐metal charge transfer (MMCT) is crucial to develop molecular devices by grafting MMCT‐based molecular arrays. Herein, we report a series of solvent‐free {Fe2Co2} compounds sharing the same cationic tetranuclear {[Fe(PzTp)(CN)3]2[Co(dpq)2]2}2+(PzTp−=tetrakis(pyrazolyl)borate, dpq=dipyrido[3,2‐d:2′,3′‐f]quinoxaline) square units but having anions with different size, including BF4−, PF6−, OTf−, and [Fe(PzTp)(CN)3]−. Intermolecular π⋅⋅⋅π interactions between dpq ligands, which coordinate to cobalt ions in the {[Fe(PzTp)(CN)3]2[Co(dpq)2]2}2+units, can be modulated by introducing different counterions, regulating the distortion of the CoN6octahedron and ligand field around the cobalt ions. This change results in different MMCT behavior. Computational analyzes reveal the substantial role of the intermolecular interactions tuned by the presence of different counteranions on the MMCT behavior.